We have successfully synthesized and structurally characterized eight novel aluminum compounds with N,O-beta-heteroarylalkenolate ligands (L) containing a CF3 group. The reactions of 3,3,3-trifluoro(dimethyl-1,3-oxazol-2-yl)propen-2-ol (H-DMOTFP), 3,3,3-trifluoro(pyridin-2-yl)propen-2-ol (H-PyTFP), and 3,3,3-trifluoro(1,3-benzthiazol-2-yl)propen-2-ol (H-BTTFP) with chloroalanes R2AlCl and RAlCl2 (R = Et, iBu) in dry aprotic solvents provided complexes displaying several types of molecular structures. Effects of ligand, solvent, and crystallization conditions were investigated. The most common and stable products were chloride complexes [AlCl(L)2] with five-coordinated aluminum centers represented by [AlCl(DMOTFP)2] (1) and [AlCl(PyTFP)2] (2). A six-coordinated aluminum complex with a coordinated THF was obtained as [AlCl(THF)(PyTFP)2] (2.THF). Complexes with preserved alkyl groups [AlR(L)2] were isolated as [AlEt(BTTFP)2] (3) and [AliBu(DMOTFP)2] (4). An intermolecular rearrangement led to an ionic complex [Al(PyTFP)2(THF)2][iBuAlCl3] (5). In the reactions of H-BTTFP, the complex 3 with two ligands, as well as molecules [AlRCl(L)] with only one ligand attached were characterized as [AlEtCl(BTTFP)] (6) and [AliBuCl(BTTFP)] (7). The thermal properties of obtained complexes were investigated by TG/DSC and HT/XRD analyses.